WO2004095128A1

WO2004095128A1 - Method of processing silver halide photographic lightsensitive material

Info

Publication number: WO2004095128A1
Application number: PCT/JP2003/005148
Authority: WO
Inventors: Toyoki Nishijima
Original assignee: Konica Minolta Photo Imaging, Inc.
Priority date: 2003-04-23
Filing date: 2003-04-23
Publication date: 2004-11-04

Abstract

A method of processing a silver halide photographic lightsensitive material that reduces staining of white background area even when processing is performed with a regenerated processing solution. In particular, a method of processing a silver halide photographic lightsensitive material, the silver halide photographic lightsensitive material comprising a support overlaid with a binder, characterized in that the binder contains iron in a proportion of 0.01 to 10 ppm and that an overflow solution of color developer occurring at the time of continuous processing after imagewise exposure of the silver halide photographic lightsensitive material is regenerated and used in the processing of the silver halide photographic lightsensitive material.

Description

Description: Processing method of silver halide photographic light-sensitive material

The present invention relates to a method for processing a silver halide photographic light-sensitive material, and more particularly, to a method for processing a silver halide photographic light-sensitive material having excellent stability in image density of a processed image using a reproduction processing solution. Background art

In recent years, the photographic industry has demanded a silver halide photographic light-sensitive material that can be rapidly processed, has high image quality, and can always maintain stable performance.

In order to achieve rapid processing in response to the current situation and needs of such markets, approaches are being made from two aspects: silver halide photographic materials and developing solutions. With regard to the developing solution, many attempts have been made to optimize the temperature and pH and to use additives such as a development accelerator. However, these methods often involve performance degradation such as an increase in capri. On the other hand, it is known that the halogen composition of a silver halide emulsion used in a silver halide photographic light-sensitive material affects the development speed. In particular, a silver halide emulsion having a high silver chloride content is used. , It is known to exhibit a significantly higher imaging speed.

It is also necessary to improve not only the silver halide emulsion but also the color-forming component such as a coupler having a high cloning rate with an oxidized color developing agent. For this reason, couplers and high-boiling organic solvents to be contained in silver halide photographic materials, color mixing prevention It is also necessary to adjust the addition of agents and anti-fading agents.

In addition, in order to speed up the development process, to reduce the cost of the development process and to reduce the amount of waste liquid, a method of reusing the used developer solution once and using it has come to be used. That is, it removes accumulated components that are harmful to photographic performance from used color developing solutions, adds missing components due to consumption, and regenerates without removing accumulated components of used color developing solution as a replenisher for color developing. There is known a regeneration treatment method in which an agent is contained and reused.

However, it has been found that in the above-mentioned regenerating process, particularly in the regenerating solution process in the rapid process, coloring of a white background portion (also referred to as "sting") is likely to occur.

As a result of various studies on the above-mentioned problems, the amount of iron contained in the binder in the silver halide photographic light-sensitive material was regulated to a specific range, so that even when a reprocessing solution was used, the white background The present inventors have found that a silver halide photographic light-sensitive material having reduced generation of stin in the present invention can be obtained, and have reached the present invention.

The treatment method using the regenerating treatment solution according to the present invention is disclosed (for example, see Patent Document 1), but there is no description specifying the iron content of the binder specified in the present invention. No mention is made of the preferred embodiment of obtaining a good white background depending on the amount of calcium and the specifications of the surfactant.

Accordingly, an object of the present invention is to provide a method for processing a silver halide photographic light-sensitive material which is excellent in whiteness of a processed image using a regenerating processing solution.

(Patent Document 1)

Japanese Patent Application Laid-Open No. Hei 6-1024 (claims) Disclosure of the invention

The above object of the present invention is achieved by each of the following constitutions.

(1) In a method for processing a silver halide photographic light-sensitive material having a binder on a support, the iron content of the binder is 0.01 to 10 ppm, and the silver halide photographic light-sensitive material is subjected to image formation. After the exposure, the overflow of the color developing solution during continuous processing is regenerated, and the regenerated color developing solution is used for processing the silver halide photographic material. Processing of silver photographic light-sensitive materials.

(2) the total calcium content of the silver halide photographic light-sensitive material, processing of silver halide photographic materials according to, characterized in that 0.5 a ^{0 1~ 1 Om g / m 2} (1) Method.

(3) The processing of the silver halide photographic light-sensitive material according to (1) or (2), wherein the silver halide photographic light-sensitive material contains an anionic surfactant having a benzene ring or a naphthalene ring. Method.

(4) At least one kind of the binder is gelatin, and a total content of the gelatin is not more than 6.2 gZm ² , wherein the binder is any one of (1) to (3). 3. The method for processing a silver halide photographic light-sensitive material according to item 1.

(5) The method for processing a silver halide photographic light-sensitive material according to any one of (1) to (4), wherein the silver halide photographic light-sensitive material contains a nonionic surfactant.

BEST MODE FOR CARRYING OUT THE INVENTION

The present invention provides a method for processing a silver halide photographic material having a binder on a support. The method according to claim 1, wherein the iron content of the binder is 0.01 to 10 ppm, and the silver halide photographic light-sensitive material is exposed imagewise and then overflowed in a color developing solution during continuous processing. The silver halide photographic light-sensitive material is processed using the regenerated color developer.

In the present invention, one of the characteristics is that the iron content of the binder used in the silver halide photographic light-sensitive material according to the present invention is from 0.01 to 10 ppm, preferably from 0.1 to 10 ppm. 0.1 to 5 ppm, and more preferably 0.01 to 3 ppm. The iron content of the binder in the present invention is the content of iron and iron ions contained in the binder, and is determined by the Pagy method (published by the Joint Council for the Test of Gelatin for Photography, 6th edition, 1989). It is measured based on the method (atomic absorption method) described in October, 1998.

In the silver halide photographic light-sensitive material according to the present invention, for example, when a plurality of different gelatins are contained as a binder, an average iron content of all gelatins contained in the silver halide photographic light-sensitive material, that is, It is defined by the mass ratio of iron in the total gelatin contained in the silver halide photographic material to the total gelatin contained in the silver halide photographic material.

When gelatin is used as the binder, ion exchange treatment using an ion exchange resin is generally performed as a method of reducing metal ions in gelatin.However, removal of trace iron ions contained in gelatin is not always necessary. It is not always effective, and methods such as the use of a chelating resin, solvent extraction, and foam separation are also used. Also, producing gelatin using a raw material having a low iron content is effective in reducing the iron content in gelatin, and further preventing the contamination of iron from production equipment in the gelatin production process. , Removal of mixed iron powder by magnet etc. It is effective for reducing the content.

A silver halide photographic material according to the present invention, all-out Rushiumu content in the coated film, but is preferably in the range of 0. 0 1~ 10 m gZm ^2, the calcium content here is calcium atom contained in the silver halide photographic material 1 m ^2, calcium ions, a calcium salt, the mass in terms of calcium atoms all compounds containing calcium, the assay ICP (I nductively C onpied Plasma) This is the value measured using emission spectrometry.

The details of this analytical method are described in “Chemical Field, Special Issue No. 127” (Nankodo, published in 1980) and VA Fassel: Anal. Chem., 46, 1110 A (1974). There is a description.

Generally, gelatin, which is advantageously used as a binder in silver halide photographic light-sensitive materials, usually contains several thousand ppm of calcium salts derived from raw materials and manufacturing processes in terms of calcium atoms. For example, a silver halide photographic light-sensitive material for direct viewing that has been put into practical use usually contains 15 mg / m ² or more of calcium. In the present invention, the total amount of calcium that is contained in all the constituent layers of the silver halide photographic light-sensitive material, arbitrary preferable in the range of 0.0 1 to 10 m g ² is 0.0 to 5. More preferably, it is in the range of 0 mg / m ² .

In the present invention, in order to reduce the total power content of the silver halide photographic light-sensitive material, a method of using gelatin having a low calcium content as a binder or a support for producing a silver halide photographic light-sensitive material can be used. A coating solution or a composition containing gelatin, such as a silver halide emulsion, a dispersion of a hydrophobic compound such as power brush, or a gelatin solution, which is contained in the coating solution, is washed with noodles, washed with dialysis, and subjected to ultrafiltration. Etc. A more desalting method may be mentioned, but it is preferable to use gelatin having a low calcium content.

In order to reduce the calcium content in gelatin, generally, ion exchange treatment is preferably used. For example, as described in JP-A-63-296035, an ion-exchange treatment is carried out by adding a gelatin solution to an ion-exchange resin, particularly for removing calcium ion, during the production or use of gelatin. Is preferably used.

Examples of gelatin having a low calcium content include acid-treated gelatin in which calcium is hardly mixed in the production process.

The gelatin used in the present invention is preferably a lime-processed gelatin subjected to an ion exchange treatment in view of the effects of the present invention. In addition, an oxidation treatment with hydrogen peroxide or the like can be performed for the purpose of reducing photographic activity.

In the silver halide photographic light-sensitive material according to the present invention, it is preferable that at least one kind of binder is gelatin, and in the present invention, the total content of gelatin is 6.2 g / m ² or less. preferably, more preferably 4. 0~6. 2 g Roh m ^2, 5. ^0~6. more preferably from 0 gZm ^2, 5. and particularly preferably 1~5. 7 gZm ² .

In the silver halide photographic light-sensitive material according to the present invention, it is preferable to use gelatin as a binder as described above. If necessary, another gelatin, a gelatin derivative, a gelatin and another polymer graft polymer, Proteins other than gelatin, sugar derivatives, cellulose derivatives, and hydrophilic colloids such as synthetic hydrophilic polymer substances such as homopolymers and copolymers can also be used.

The silver halide photographic light-sensitive material according to the present invention has a benzene ring or a naphthalene ring. The anionic surfactant preferably contains an anionic surfactant having a benzene ring or a naphthalene ring and an anionic group. The anionic surfactant is not particularly limited as long as the anionic surfactant has a benzene ring or a naphthalene ring and an anionic group. Those having a group are preferred. Further, a surfactant in which a sulfonic acid group is directly substituted on a benzene ring or a naphthalene ring is preferable. Addition of these compounds can contribute to stabilization of coupler dispersion.

Preferred compounds include the following, but the present invention is not limited to these surfactants.

S-1: Sodium dodecylbenzenesulfonate

S-2: sodium octadecylbenzenesulfonate

S-3: isopropyl naphthalene sulfonic acid

The anionic surfactant according to the present invention may be added to any layer in the silver halide photographic light-sensitive material, and the amount of addition may be appropriately determined depending on the design of various characteristics of the silver halide light-sensitive material. It is determined.

Further, the silver halide photographic material according to the present invention preferably contains a nonionic surfactant.

As the nonionic surfactant used in the silver halide photographic light-sensitive material according to the present invention, those represented by the following formula (N) are preferred.

General formula (N)

R— (G) m—X

In the above general formula (N), R represents an alkyl group (including those having a substituent), an alkoxy group (including those having a substituent), an alkenyl group (including those having a substituent), Aryl group (including those having a substituent), Or an aryloxy group (including those having a substituent). G represents a divalent linking group, X represents a hydrophilic group of a nonionic group, and m represents 0 or 1.

G is preferably an alkylene group (including those having a substituent, such as an ethylene group and a trimethylene group), and an arylene group (including those having a substituent, such as a propyl group and a phenylene group). Or an arylalkylene group (including those having a substitution group, for example, a phenylethylene group). These groups include an oxygen atom, an ester group, an amide group, a sulfonyl group, and a sulfur atom. Also included are divalent linking groups interrupted by such heterologous atoms or heterologous groups.

The non-specific group represented by X is, for example, 1 (B-0) _n -Rs. Where B represents one CH ₂ CH ₂ —, one CH ₂ CH ₂ CH ₂ —, one CH ₂ CH (OH) — CH ₂ — or one CH (CH ₃ ) —CH ₂ —, and n is poly. It represents the average degree of polymerization of the oxyalkylene group and is an integer of 1 to 50. R s represents a hydrogen atom, an alkyl group including a substituent, or an aryl group including a substituent.

Specific examples of typical nonionic surfactants according to the present invention are shown below, but those used in the present invention are not limited thereto.

N-1 N-2

H- ^ CF ^ j ~ CH ₂ 0— (CH ₂ CH ₂ O) ₁₀ -HC ₈ F ₁₇ CH ₂ CH ₂ 0— (CH ₂ CH ₂ 0) ₁₂ _H

8

N— 3

C ₈ F ₁₇ SO _z N— (CH ₂ CH ₂ 0) “— H 8 ^H 17--0- (CH ₂ CH ₂₀ ) ₈ H N— 5 N-6

ceHi "O-(CH ₂ CH ₂ 0) ₁₄ HC ₁₃ H ₂₇ 0— (CH ₂ CH ₂ 0) ₆ H

N-7 N-8

C ₁₃ H ₂₇ 0— (CH ₂ CH ₂₀ ) ₁₄ HC ₁₄ H ₂₃ 0— (CH ₂ CH ₂₀ ) ₄ H

N— 9 N— 10

C14H29O— (CH2CH20) 2QH C ₈ H ₁₇ S so0 ₂₂ --N (CH ₂ CH ₂ O) ₁₀ H

C3H7

N-11 N-12

C ₈ H ₁₇ S0 ₂ -N (CH ₂ CH ₂ 0) _1S H

C ₁₁ H ₂ 3COO- CH2CH ₂ 0) — H

C3H7 a

N-13 N— 14

N-15 N-16

C ₈ H ₁₇ 0 ~ ("CH ₂ CH ₂ 0)" H Ci ₆ H ₃₃ 0-(-CH2CH ₂ 0) ^ H

N-17 N— 18

N-22 N-23

^ CH ₂ CH ₂ 0)--H

C ₁₃ H ₂₇ CON C12H25S ~ (OH2CH2 JH

^ CH ₂ CH ₂ o)-H 16

a + b = 15

_{_{N- 24 C 12 H 2 sO -}} (- CH - CH 2 0-h- CH 2 CH 2 0) - H

CH ₃

A silver halide photographic material according to the present invention, the amount of the nonionic surfactant, 1 m ² per silver halide photographic light-sensitive material, 0. l~1000m g is preferably, 0. 5 to 300 mg More preferably, 1.0 to 150 mg is particularly preferable.

As the nonionic surfactant, each of the nonionic surfactants may be used alone, or two or more nonionic surfactants may be used in combination.

The silver halide used in the silver halide emulsion layer according to the present invention includes any silver halide such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide, silver chloroiodide and the like. The silver halide grains used in the silver halide photographic light-sensitive material according to the present invention have a silver chloride content of 95 mol% or more, a silver bromide content of 5 mol% or less, and iodine. It is preferable that the silver halide content is 0.5 mol% or less. More preferably, it is silver chlorobromide having a silver bromide content of 0.1 to 2 mol%. The silver halide particles may be used alone or as a mixture with other silver halide particles having different compositions. It may be used by mixing with silver halide grains having a silver chloride content of 95 mol% or less.

In a silver halide layer containing silver halide grains having a silver chloride content of 95 mol% or more, a silver chloride content of 95 mol% of all silver halide grains contained in the emulsion layer is contained. % Of the silver halide grains is 60% by mass or more, preferably 80% by mass or more. The composition of the silver halide grains may be uniform from the inside to the outside of the grains, or the inside and outside compositions of the grains may be different. When the inside and outside compositions of the particles are different, the composition may change continuously or may be discontinuous.

The silver halide grains according to the present invention may have any shape. One preferable shape is a cube having a (100) plane as a crystal surface. Also, U.S. Pat. Nos. 4,183,756, 4,225,666, Japanese Patent Application Laid-Open No. 55-26589, Japanese Patent Publication No. 55-42737, and The Journal of Ob-Photography. Particles having shapes such as octahedron, tetradecahedron, and dodecahedron can be obtained by methods described in documents such as J. P hotog r. S ci. 21, 39 (l973). You can also make and use this. Further, particles having a twin plane may be used.

As the silver halide grains according to the present invention, grains having a single shape may be used. Alternatively, particles of various shapes may be mixed.

The grain size of the silver halide grains according to the present invention is not particularly limited, but is preferably 0.1 to 1.2 μm, more preferably 0.1 to 1.2 μm, in consideration of other photographic properties such as rapid processing and sensitivity. Is in the range of 0.2 to 1.0 m. The particle size can be measured by various methods generally used in the technical field. As a typical method, there is “Label size analysis method” of ASTM Symposium (ASTM Symposium “On” Light ”Microscope, 94-L22, 1955) or“ Theory of Photographic Process No. 3 Edition "(co-authored by Mies and James, Chapter 2, published by Macmillan, 1966).

This particle size can be measured using the projected area of the particle or its approximate diameter. If the particles are substantially uniform in shape, the particle size distribution can represent this quite accurately as diameter or projected area.

The particle size distribution of the silver halide grains according to the present invention may be polydisperse or monodisperse. Monodisperse silver halide grains having a coefficient of variation of preferably 0.22 or less, more preferably 0.15 or less are preferred. Here, the coefficient of variation is a coefficient representing the width of the particle size distribution, and is defined by the following equation.

Coefficient of variation = SZR (where, S is the standard deviation of the particle size distribution, and R is the average particle size.) The particle size referred to here is the diameter of a spherical silver halide particle, or a cube. In the case of particles having a shape other than spherical or spherical, it represents the diameter when the projected image is converted into a circular image of the same area. Various methods known in the art can be used as an apparatus and a method for preparing a silver halide emulsion.

The silver halide emulsion according to the present invention may be obtained by any of an acidic method, a neutral method, and an ammonia method. The particles may be grown at one time Alternatively, the seed particles may be grown after they are made. The method of making the seed particles and the method of growing them may be the same or different.

The form of reacting the soluble silver salt with the soluble halide salt may be any of a forward mixing method, a reverse mixing method, a simultaneous mixing method, a combination thereof, and the like, but a method obtained by the simultaneous mixing method is preferable. Furthermore, Japanese Patent Application Laid-Open

The pAg controlled double-jitter method described in 54-4852 No. 1 and the like can also be used.

Further, a water-soluble silver salt and a water-soluble silver salt were obtained from an addition device disposed in a reaction mother liquor described in JP-A-57-92523 and JP-A-57-92525. A device for supplying an aqueous solution of a halide salt, a device for continuously changing the concentration of an aqueous solution of a water-soluble silver salt and a water-soluble halide salt described in German Published Patent Application No. 2,921,164, etc. Take the reaction mother liquor out of the reactor as described in JP-B-56-501017, etc. and concentrate by ultrafiltration to form grains while keeping the distance between silver halide grains constant. An apparatus or the like may be used.

Further, if necessary, a silver halide solvent such as thioether may be used. Further, a compound having a mercapto group, a nitrogen-containing heterocyclic compound or a compound such as a sensitizing dye may be added at the time of forming silver halide grains or after the completion of grain formation.

A known method can be used to reduce the silver halide emulsion according to the present invention. For example, a method of adding various reducing agents can be used, a method of ripening under a high silver ion concentration condition, or a method of ripening under a high pH condition can be used.

The reducing agent used for the reduction sensitization of the silver halide emulsion according to the present invention includes: Examples thereof include stannous salts such as tin, borane such as tri-tert-butylamine borane, sulfites such as sodium sulfite and sulfite, reductones such as ascorbic acid, and thiourea dioxide. Of these, thiourea dioxide, ascorbic acid and its derivatives, and sulfites can be preferably used. Compared with the case where reduction sensitization is performed by controlling the silver ion concentration and pH during ripening, the method using a reducing agent as described above is preferable because of excellent reproducibility.

These reducing agents may be dissolved in a solvent such as water or alcohol and added to the silver halide emulsion for ripening, or may be added during the formation of silver halide grains to perform reduction sensitization simultaneously with the formation of the grains. You may.

The amount of adding these reducing agents are p H of the silver halide emulsion, it is necessary to adjust as etc. silver ion concentration, typically, 1 per silver halide emulsion 1 mole X 1 0- ⁷ ~ 1 X 1 0- ² mol is preferred.

After reduction sensitization, a small amount of oxidizing agent may be used to modify the reduction sensitizing nucleus or deactivate the remaining reducing agent. Examples of the compound used for such a purpose include potassium hexacyanoferrate (III), promosuccinimide, p-quinone, potassium perchlorate, and hydrogen peroxide.

The silver halide emulsion according to the present invention can be subjected to reduction sensitization, and can be used in combination with a sensitization method using a gold compound and a sensitization method using a chalcogen sensitizer. As the chalcogen sensitizer applied to the silver halide emulsion according to the present invention, an iris sensitizer, a selenium sensitizer, a tellurium sensitizer, or the like can be used, but an io sensitizer is preferable. Examples of the sensitizers are sulphate sulfate, arylthiothiolamine, arylisothiocyanate, cystine, and p-toluenethiol. Fonates, rhodanine and the like.

As the gold sensitizer applied to the silver halide emulsion according to the present invention, various gold complexes such as chloroauric acid, gold sulfide, gold thiocyanate and the like can be added. Examples of the ligand compound to be used include dimethyl rhodanine, thiocyanic acid, mercaptotetrazol, and mercaptotriazole. Dose use of the gold compound, the kind of silver halide emulsion, the type of compound used, but connexion not uniform due to such aging conditions, is usually 1 mol of silver halide per 1 X 1 0- ⁴ mol ~ 1 X It is preferably from 10 to ⁸ mol. More preferably, the molar ratio is from 1 × 1 CT to ⁵ × 1 × 108 mol.

The silver halide emulsion according to the present invention includes a known silver halide emulsion for the purpose of preventing capri generated during the process of preparing a silver halide photographic material, reducing performance fluctuation during storage, and preventing capri generated during development. Capri inhibitors and stabilizers can be used. Examples of the compound that can be used for such a purpose include a compound represented by the general formula (II) described in the lower section of page 7 of JP-A-2-14636. Are the compounds of (IIa-1) to (IIa-8), (IIbl) to (IIb_7) described on page 8 of the same publication, and 1- (3-methoxythiene). G) 15-mercaptotetrazole and the like. These compounds are added in a step such as a step of preparing silver halide emulsion grains, a step of chemical sensitization, a step of preparing a coating solution or the like at the end of a step of chemical sensitization according to the purpose. When performing these presence in the chemical增感compounds preferably used in an amount of about 1 X 10- ⁵ mol ~ 5 X 1 0- ⁴ mol per mol of silver halide. When added at the completion of chemical sensitization, the amount of 1 X 1 CT ⁶ mol ~ 1 X 1 0 ^_2 mol per mol of silver halide is preferred, 1 X 1 CT ⁵ mol ~ 5 X 10- ³ mole of More preferred. In the coating solution preparation step, when added to the silver halide emulsion layer, the amount of 1 X 1 0- ⁶ mol to about 1 X 1 0- ¹ mol per mol of silver halide preferably, 1 X 1 0 _ ⁵ mol ~ 1 X 1 0- ² moles is more preferable. When it is added to a layer other than the silver halide emulsion layer, the amount in the coating film is preferably about 1 × 10 to ⁹ mol to 1 × 10 to ³ mol.

When the silver halide photographic light-sensitive material according to the present invention is used as a color photographic light-sensitive material, the silver halide photographic light-sensitive material may be used in combination with a yellow coupler, a magenta coupler, and a cyan coupler in a wavelength range of 400 to 900 nm. It has a layer containing a silver halide emulsion spectrally sensitized to a specific region. The silver halide emulsion contains one or more sensitizing dyes in combination.

As the spectral sensitizing dye used in the silver halide emulsion according to the present invention, any of known compounds can be used. Examples of the blue-sensitive sensitizing dye are described in Japanese Patent No. 28388722. 108- of the book: BS1-1-8 described on page L09 can be preferably used alone or in combination. As the green photosensitive sensitizing dye, GS-11 to 5 described on page 110 of the same specification are preferably used. As the red light-sensitive dye, R S — 1 to 8 described on pages 11 to 11 of the same specification are preferably used. When exposing the silver halide photographic light-sensitive material according to the present invention to a printer using a semiconductor laser, it is necessary to use a infrared-sensitive dye which is sensitive to infrared rays. The dyes of IRS-1 to 11 described on pages 12 to 14 of JP-A No. 425,950 / 1990 are preferably used. It is preferred to use supersensitizers SS-1 to SS-9 described in pages 14 to 15 of the same publication in combination with these dyes.

When exposing the silver halide photographic light-sensitive material according to the present invention using a laser For this purpose, using an exposure apparatus using a semiconductor laser is advantageous in terms of miniaturization of the apparatus. In scanning exposure, the exposure time per pixel corresponds to the exposure time actually received by the silver halide emulsion.However, in the case of scanning exposure with one laser beam, the exposure time per pixel is In the spatial change of the light intensity, the point where the light intensity reaches the maximum value of 1Z2 is defined as the outer edge of the light beam. When the distance between two intersecting points is defined as the diameter of a light beam, the (exposure time per pixel) can be considered as (light beam diameter) / (scanning speed). As the exposure time per pixel becomes shorter, the relationship between the exposure time and the color density tends to become more complicated. The present invention is particularly effective when an apparatus having a shorter exposure time per pixel is used.

Examples of laser printers that can be applied to such a system include, for example, JP-A-55-4071, JP-A-59-11062, JP-A-63-19977, JP-A-2-74942, and JP-A-2-74942. No. 236583, Japanese Patent Publication No. 56-14963, No. 56-40822, European Regional Patent No. 77,410, Electronic and Telecommunications Department Joint Technical Report 80, No. 244, and Movie and TV Technology Journal 1984/6 (382), 34 ~ 36 pages.

In the silver halide photographic light-sensitive material according to the present invention, dyes having absorption in various wavelength ranges can be used for the purpose of preventing irradiation and halation. For this purpose, any of known compounds can be used. Particularly, as dyes having absorption in the visible region, A1-1-118 described in Japanese Patent No. 2838722, pages 117 to 118, can be used. The dye of the formula (I), (I1) and (III) described in the lower left column on page 2 of JP-A-11-280750 are preferably used as the infrared absorbing dye. Has preferred spectral characteristics, and silver halide photographic milk It is preferable because it does not affect the photographic properties of the agent and does not stain due to residual color. Specific examples of preferred compounds include the exemplified compounds (1) to (45) listed in the lower left column of page 3 to the lower left column of page 5 of the same publication.

The coupler used in the silver halide photographic light-sensitive material according to the present invention includes a coupling product having a spectral absorption maximum wavelength in a wavelength region longer than 340 nm by a coupling reaction with an oxidized form of a color developing agent. Any compound capable of forming a dye can be used, but a yellow coupler having a spectral absorption maximum wavelength in the wavelength range of 350 to 500 nm, and a spectral absorption in the wavelength range of 500 to 600 nm Typical examples are a magenta coupler having a maximum wavelength and a cyan coupler having a spectral absorption maximum wavelength in a wavelength range of 600 to 700 nm.

An example of an yellow coupler that can be preferably used in the silver halide photographic light-sensitive material according to the present invention includes a compound represented by the general formula (Y-1) described on page 8 of Japanese Patent No. 2916702. Mention may be made of the couplers represented. Specific compounds include those described as YC-1 to YC-9 on pages 9 to 11 of the same specification. Among them, YC-8 and YC-9 described on page 11 of the same specification are preferable because they can reproduce yellow with a preferable color tone. Examples of magenta couplers include couplers represented by general formulas (M-I) and (M-II) described in page 29 of Japanese Patent No. 2916702. Specific compounds include those described as MC-1 to MC-11 on pages 13 to 16 of the same specification. Among them, MC-8 to MC-11 described in pages 15 to 16 of the same specification are excellent in reproducing colors from blue to purple and red, and are also excellent in detail depiction, and thus are preferable. The silane coupler preferably used in the silver halide photographic light-sensitive material according to the present invention includes a compound represented by the general formula (C) described in page 29 of Japanese Patent No. 2916702. —I) and couplers represented by (C-II). Specific compounds include those described as CC-11 to CC-9 on pages 18 to 21 of the same specification.

When the oil-in-water type emulsion dispersion method is used to add the coupler used in the silver halide photographic light-sensitive material according to the present invention, a water-insoluble high-boiling organic solvent having a boiling point of 150 or more is usually used. If necessary, dissolve using a low boiling point or water-soluble organic solvent in combination, and emulsify and disperse in a hydrophilic binder such as an aqueous gelatin solution using a surfactant. As the dispersing means, a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic disperser, or the like can be used. After the dispersion, or simultaneously with the dispersion, a step of removing the low boiling organic solvent may be added. As the high-boiling organic solvent that can be used for dissolving and dispersing the coupler, phthalic acid esters such as octyl phthalate, and phosphoric esters such as tricresyl phosphite are preferably used.

Instead of using a high-boiling organic solvent, a coupler and a water-insoluble and organic solvent-soluble polymer may be dissolved in a low-boiling or water-soluble organic solvent, if necessary, and a hydrophilic binder such as an aqueous gelatin solution may be used. A method of emulsifying and dispersing by a variety of dispersing means using a surfactant therein may be employed. As the water-insoluble and organic solvent-soluble polymer used at this time, poly (N-t-butylacrylamide) and the like can be mentioned.

For the purpose of shifting the absorption wavelength of the color-forming dye, the compound (d-11) described on page 33 of Japanese Patent No. 2916702 and the compound (A '-1) and the like. In addition, the fluorescent dye releasing compounds described in U.S. Pat. Nos. 4,774,187 can also be used. The coating amount of the coupler is not particularly limited as long as a sufficiently high concentration can be obtained, but is preferably 1 ^× 10 ^{-3 to} 5 mol, more preferably 1 × 10 ^_ per mol of silver halide. It is used in the range of ² to 1 mol.

In the present invention, it is preferable to add an oil-soluble dye. The oil-soluble dye refers to an organic dye having a solubility in water at 20 ° C. of 0.01 or less, and is preferably a compound having a molecular absorption coefficient of 20,000 or more at a maximum absorption wavelength at a wavelength of 400 nm or more. Preferred compounds include the compounds shown on page 26 of Japanese Patent No. 2799580. Specific examples of preferable compounds include Compounds 1 to 27 described on page 29 or page 32 of the above specification. Of these, compounds 4 and 9 are particularly preferred. Oil-soluble dye is preferably added to the non-photosensitive layer, it is preferably added in an amount of 0. 05~5m gZm ^2.

Any material may be used as the reflective support according to the present invention, such as a white pigment-containing polyethylene-coated paper, baryta paper, a vinyl chloride sheet, a polypropylene containing a white pigment, and a polyethylene terephthalate support. Etc. can be used.

Among them is a support having a polyolefin down resin layer on both surfaces, and mass of preferably ² 17 g / m 2 or less of the support, more preferably ² 1 5 gZm 2 below. Further, the polyolefin resin layer preferably contains a white pigment.

As the white pigment used in the reflective support according to the present invention, an inorganic or organic white pigment can be used, and an inorganic white pigment is preferably used. For example, sulfates of alkaline earth metals such as barium sulfate, carbonates of alkaline earth metals such as calcium carbonate, silicas such as finely divided gay acid and synthetic gateates, calcium silicate, alumina, Alumina hydrate, titanium oxide, zinc oxide, talc, clay, etc. No. The white pigment is preferably barium sulfate or titanium oxide. The amount of the white pigment contained in the water-resistant resin layer on the surface of the reflective support according to the present invention is preferably 10% by mass or more as a content in the water-resistant resin layer, and more preferably 13% or more. The content is preferably at least 15 mass%, more preferably at least 15 mass%. The degree of dispersion of the white pigment in the water-resistant resin layer of the paper support according to the present invention can be measured by the method described in JP-A-2-28640. When measured by this method, the degree of dispersion of the white pigment is preferably 0.20 or less, more preferably 0.15 or less, and preferably 0.10 or less, as the coefficient of variation described in the publication. More preferably, it is.

The silver halide photographic light-sensitive material according to the present invention may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. on the support surface, if necessary, and then directly or undercoating (adhesion of the support surface, antistatic property) Or one or more subbing layers to improve the properties, dimensional stability, rub resistance, hardness, antihalation properties, frictional properties or other properties.

When coating a photographic light-sensitive material using a silver halide emulsion, a thickener may be used to improve coatability. As a coating method, an extrusion coating and a force coating which can simultaneously apply two or more kinds of layers are particularly useful.

Generally, silver halide ions and organic compounds (for example, sensitizing dyes and inhibitors) are eluted from the silver halide photographic light-sensitive material into the developer from the silver halide light-sensitive material during the development process. However, it is known that it accumulates in the developer, thereby suppressing the development reaction.

Therefore, reduce the amount of eluted substances in the developer and keep the concentration constant Is required. In a normal developing method, halide ions and organic compounds are eluted from a silver halide photographic material into a developing solution, and further, a developing agent, a preservative and an alkaline agent are consumed and reduced. Therefore, a replenisher is added to the developer in order to keep these concentrations substantially constant and maintain the developing characteristics, and the amount of the replenisher is allowed to flow out of the developer tank system as an overflow solution, and is added to the developer. The accumulated halide ions and organic compounds are removed from the system. In addition, the replenisher has been used to replenish the deficient components such as consumed developing agent and the like, and the developer concentration has been kept constant.

In the present invention, the silver halide photographic light-sensitive material is regenerated from an overflow of a color developing solution that is generated when the silver halide photographic light-sensitive material is continuously processed after the imagewise exposure, and is reused in the processing of the silver halide photographic light-sensitive material. It is also referred to as a reproduction processing method). In the present invention, a continuous processing is carried out by processing a silver halide photographic light-sensitive material having a characteristic of containing an alkyl alcohol derivative compound in the above-mentioned light-sensitive layer or non-light-sensitive layer by the above-mentioned reproduction processing method. In addition, a stable image density can always be obtained. In addition, by reusing the developing solution, cost reduction and environmental load reduction can be achieved.

As a method for regenerating the color developer, any known method may be used. For example, regeneration using the ion exchange resin described in JP-A-3-69936, JP-A-3-194552, JP-A-55-144240, JP-A-53-132343, JP-A-57-146249, and JP-A-61-95352. And a regeneration method in which a deficient component is added as a regenerating agent without particularly removing components eluted in a developer described in JP-A-3-174154, JP-A-51-85722, and JP-A-54-37731. No. 56-1049, No. 56-27142, No. 56-33644, No. 56-149036, No. 61-10199, No. 61-52459 A method using electrodialysis is exemplified.

Of these, a regeneration method using an ion exchange resin and a regeneration method using a regenerant are preferable from the viewpoint of maintainability, cost and ease of use.

As the aromatic primary amine developing agent used in the color developer according to the present invention, a known compound can be used. Examples of these compounds include the following compounds.

CD-I: N, N—Jetilou p—Fenylenediamine

CD-2: 2-Amino-5-Jetylamino Toluene

CD-3: 2-amino-1 5— (N-ethyl-N-laurylamino) Toluene CD-4: 4-1-1 (N-ethyl-1 N— (; 8-hydroxyxethyl) amino) aniline

CD-5: 2-Methyl-41- (N-ethyl-N- (y3-hydroxyhydryl) amino) anilin

CD-6: 4-Amino-3-methyl-N- (β- (methanesulfonamide) ethyl) aniline

CD-7: N— (2-amino-5-ethylethylaminophenyl) methane sulfonamide

CD-8: N, N_dimethyl-p-phenylenediamine

CD-9: 4-amino-3-ethyl-N-ethyl-N-methoxylaniline

CD—10: 4-Amino-3-N-methyl-N-ethyl-N— (3-ethoxyethoxy) anilin

CD-I1: 4-amino_3—methyl-1-N—ethyl-N — (/ 3-butoxy Color developing agent used in the chill) Aniri emissions present invention is usually used in the developing solution 1 liter per 1 X 1 0 one ² ~ ² X 10- ¹ mols, from the viewpoint of rapid processing color development preferably used in the liquid 1 liter per 1.5 X 10_ ² ~2 X 10- ¹ mols. The color developing agent used in the method of processing a silver halide photographic light-sensitive material of the present invention may be used alone, or may be used in combination with other known p-phenylenediamine derivatives. A preferred developer in the method for processing a silver halide photographic light-sensitive material of the present invention is substantially free of benzyl alcohol. Here, “substantially not contained” means that benzyl alcohol has a content of 2 m 1 or less, and it is most preferred that the benzyl alcohol is not contained at all in the present invention.

The color developing solution used in the present invention may contain the following developing solution components in addition to the above components. Alkali agents such as sodium hydroxide, potassium hydroxide, sodium metaborate, potassium metaborate, sodium phosphate, potassium phosphate, borax, and silicate are used alone or in combination. They can be used in combination as long as no precipitation occurs and the pH stabilizing effect is maintained. Furthermore, for the purpose of dispensing, or for the purpose of increasing ionic strength, various types of sodium hydrogen phosphate, hydrogen phosphate phosphate, sodium bicarbonate, sodium bicarbonate phosphate, borate, etc. Salts can be used.

Further, in the color developing solution according to the present invention, JP-A-63-146043, JP-A-63-146042, JP-A-63-146041, and JP-A-63-146043, in place of hydroxylamin conventionally used as a preservative, are used. Nos. 63-146040, 63-135938, 63-118748, and hydroxylamine derivatives and hydroxams described in JP-A-64-62639, JP-A-1-303438, etc. Acids, hydrazines, hydrazides, phenols, hydroxyketones, aminoketones, sugars, monoamines, diamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamides Compounds and condensed amines are preferably used as organic preservatives.

These compounds can be used in combination with the conventionally used hydroxylamine and the organic preservative, but it is preferable not to use hydroxylamine from the viewpoint of developing properties.

Furthermore, if necessary, a development accelerator can be used. Examples of development accelerators include various pyridinium compounds represented by U.S. Pat. Nos. 2,648,604 and 3,671,247 and Japanese Patent Publication No. 44-9503, and other cationic compounds. Cationic dyes such as phenosafranine; neutral salts such as thallium nitrate; U.S. Pat. Nos. 2,533,990; 2,531,832; 2,950,970; Non-ionic compounds such as polyethylene glycol and its derivatives and polythioethers described in JP-B-57,127 and JP-B-44-9504, organic solvents and organic amines, organic amines, ethanolamines, ethylene-diamines and the like described in JP-B-44-9509. Diethanolamine, triethanolamine and the like are included. Also, phenethyl alcohol described in U.S. Pat. No. 2,304,925 and others, acetylene glycol, methylethyl ketone, cyclohexanone, pyridine, ammonia, hydrazine, thioethers, amines And the like.

Further, the color developing solution used in the present invention may be, if necessary, ethylene glycol, methyl cellulose solvent, methanol, acetone, dimethylformamide, / 9-cyclodextrin, and other Japanese Patent Publication No. 47-33378. No. 44-9509 The compounds described in each publication can be used as an organic solvent for increasing the solubility of the developing agent.

Further, an auxiliary developer can be used together with the developing agent. These auxiliary developers include, for example, N-methyl-p-aminophenol sulfate, phenylidone, N, N'-getyl-p-aminophenol hydrochloride, N, N, Ν ', N'-tetramethyl One p-phenylenediamine hydrochloride and the like are known, and the addition amount thereof is usually 0.01 to 1.0 Og per liter of the developer. In addition, if necessary, a competing coupler, a fogging agent, a development inhibitor releasing type power blur (a so-called DIR coupler), a development inhibitor releasing compound, and the like can be added.

Furthermore, various additives such as other anti-stin agents, anti-sludge agents, and layering effect promoters can be used.

Each component of the color developing solution can be prepared by sequentially adding and stirring a certain amount of water. In this case, the component having low solubility in water can be added by mixing with the above-mentioned organic solvent such as triethanolamine. More generally, a color solution used in the present invention is prepared by adding a concentrated aqueous solution containing a plurality of components each of which can stably coexist, or a solution prepared in advance in a small container in a solid state to water, and stirring the solution. A developer can also be prepared.

Sulfite concentration of the color developing solution according to the present invention, 1 X 1 0- ² mol to less favorable preferable. Particularly good in the 7 X 1 0- ³ mol ZL below contains zero, preferably during less than 5 X 1 0 _ ³ moles ZL especially including 0.

In the present invention, the above color developer can be used in an arbitrary pH range, but from the viewpoint of rapid processing, the pH is preferably pH 9.5 to 13. Used in the range of H9.8-12.0.

The processing temperature of color development used in the present invention is preferably 35 ° C. or more and 70 ° C. or less. The higher the temperature, the shorter the processing time is possible, which is preferable. However, from the viewpoint of the stability of the processing solution, the lower the temperature, the more preferable. The color development time is preferably within 45 seconds in the present invention.

The processing step essentially comprises a color developing step, a bleach-fixing step, and a rinsing step (including a stabilizing treatment in place of rinsing), but steps with additional or equivalent meanings as long as the effects of the present invention are not impaired. Can be replaced by For example, the bleach-fixing step can be separated into a bleaching step and a fixing step, or a bleaching step can be performed before the bleach-fixing step. As a processing step used in the image forming method of the present invention, a bleach-fixing step is preferably provided immediately after the color developing step.

The bleaching agent that can be used in the bleach-fixing solution used in the present invention is not limited, but is preferably a metal complex salt of an organic acid. The complex salt is a complex salt in which an organic acid such as polycarboxylic acid, aminopolycarboxylic acid, or oxalic acid or citric acid is coordinated to a metal ion such as iron, cobalt, or copper. Most preferred organic acids used to form such metal complexes of organic acids include polycarboxylic acids or aminopolycarboxylic acids. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts.

Specific examples of these compounds include the compounds [2:] to [20] described in JP-A No. 125252 / pages 58-59.

These bleaches are used in an amount of 5 to 450 g, preferably 20 to 250 g, per liter of the bleach-fix solution. In addition to the bleaching agent as described above, A composition solution containing a silver logenogen fixing agent and, if necessary, a sulfite as a preservative is applied. Also, a bleach-fixing solution having a composition in which a large amount of a halide such as ammonium bromide is added in addition to the ethylenediaminetetraacetate (111) bleaching agent and the silver halide fixing agent, and ethylenediaminetetraacetic acid A special bleach-fixing solution having a composition comprising a combination of an iron (III) bleach and a large amount of a halide such as ammonium bromide can be used. As the halide, in addition to ammonium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide and the like can be used.

Examples of the silver halide fixing agent contained in the bleach-fixing solution include compounds which react with silver halide to form a water-soluble complex salt as used in ordinary fixing processing, for example, thiosulfuric acid, Typical examples thereof include thiosulfates such as sodium sulfate and ammonium thiosulfate, potassium thiocyanate, sodium thiocyanate, thiocyanates such as ammonium thiocyanate, thiourea, and thioether. These fixing agents are used in an amount of at least 5 g per liter of the bleach-fixing solution and in a dissolvable range, but generally used in an amount of 70 to 250 g. The bleach-fixing solution contains boric acid, borax, sodium hydroxide, sodium hydroxide, sodium carbonate, sodium carbonate, sodium bicarbonate, sodium bicarbonate, acetic acid, sodium acetate. Various pH buffers such as ammonium hydroxide can be used alone or in combination of two or more. Furthermore, various fluorescent whitening agents, antifoaming agents or surfactants can be contained. In addition, preservatives such as bisulfite adducts of hydroxylamine, hydrazine and aldehyde compounds, organic chelating agents such as aminopolycarboxylic acid, and stabilizers such as nitro alcohol and nitrate; Organic solvents such as methanol, dimethylsulfonamide and dimethylsulfoxide can be appropriately contained. The bleach-fixing solution used in the present invention includes Japanese Patent Publication No. 46-280, Japanese Patent Publication No. 45-8506, Japanese Patent Publication No. 46-556, Belgian Patent No. 770910, Japanese Patent Publication No. 45-8836, Various bleaching accelerators described in JP-A-53-9854, JP-A-54-71634 and JP-A-49-42349 can be added.

The pH of the bleach-fix solution is used at pH 4.0 or higher, but is generally used in the range of pH 4.0 to 9.5, preferably pH 4.5 to 8.5. Most preferably, it is used in the pH range of 5.0 to 8.5. Use at a temperature of 80 ° C or less, preferably 55 ° C or less, while suppressing evaporation. The processing time for bleach-fixing is preferably from 3 to 45 seconds. In the developing process used in the present invention, a water washing process is performed subsequent to the color developing and bleach-fixing steps. The pH of the washing water applicable to the present invention is in the range of 5.5-10.0. The treatment temperature of the water washing treatment is preferably 15 to 60 ° C, more preferably 20 to 45 ° C. Further, the time of the water washing treatment is preferably 5 to 90 seconds. In the case of performing the water washing treatment in a plurality of tanks, it is preferable that the treatment is performed in a shorter time in the front tank and the treatment time is longer in the rear tank. In particular, it is preferable that the treatment be performed sequentially with a treatment time 20 to 50% longer than that of the preceding tank.

As a development processing apparatus used in the method for processing a silver halide photographic light-sensitive material of the present invention, any known apparatus may be used. Specifically, even in the case of a roller-transport type in which a silver halide photographic light-sensitive material is conveyed between rollers arranged in a processing tank, the silver halide photographic light-sensitive material is fixed to a belt and conveyed. An endless belt method may be used, in which a processing tank is formed in a slit shape, a processing solution is supplied to this processing tank, and a silver halide photographic photosensitive material is conveyed. A method of spraying a treatment liquid, a spray method of spraying the treatment liquid, a web method by contact with a carrier impregnated with the treatment liquid, and a method of using a viscous treatment liquid can also be used. In the present invention, a large amount of photosensitive material is processed and run in these color development to drying steps, and elution of components from the photosensitive material into the processing solution and contamination between processing tanks and evaporation of the processing solution are saturated. This is especially effective when the treatment is performed after the temperature is stabilized.

In the present invention, the time from exposure to development may be any, but it is preferable that the time be short in order to shorten the overall processing time.

Next, the present invention will be described specifically with reference to examples, but embodiments of the present invention are not limited thereto.

<< Silver halide color photographic light-sensitive material: Preparation of sample 101 >>

(Preparation of silver halide emulsion)

Each silver halide emulsion was prepared by the following method.

(Preparation of red-sensitive silver halide emulsion)

In 1 liter of a 2% aqueous gelatin solution kept at 40 ° C., the following (solution A) and (solution B) were mixed for 30 minutes while controlling pAg to 7.3 and pH to 3.0. The following (Solution C) and (Solution D) were simultaneously added over 180 minutes while controlling the pAg at 8.0 and the pH at 5.5. At this time, the control of pAg was performed by the method described in JP-A-59-45437, and the control of pH was performed using sulfuric acid or an aqueous sodium hydroxide solution.

(A liquid)

Sodium chloride 3.42 g Potassium bromide 0.03 g 200ml with water

(Solution B)

Silver nitrate 10 g Add water 200ml

(C solution)

Sodium chloride 102.7 g K ₂ Ir C 1 βX 10 ¹⁸ mol / mol A g K ₄ ^Fe (CN) 2 X 10 ^_5 mol / mol A g ^Potassium bromide 1.0 g Water In addition 600ml

(D solution)

After adding 300 g of silver nitrate and adding 600 ml of each of the above solutions, desalting was performed using a 5% aqueous solution of Demol N and 20% aqueous magnesium sulfate manufactured by Kao Atlas, and gelatin was added. When mixed with an aqueous solution, a silver halide emulsion EMP-1 which is a monodisperse cubic emulsion having an average particle size of 0.40 m, a coefficient of variation of the particle size distribution of 0.07, and a silver chloride content of 99.5 mol% was obtained. Was.

Next, the average particle size was determined in the same manner as in the silver halide emulsion EMP-1, except that the addition times of the above (Solution A) and (Solution B) and the addition times of (Solution C) and (Solution D) were changed. A silver halide emulsion EMP-1B was obtained as a monodisperse cubic emulsion having 0.38, a coefficient of variation in particle size distribution of 0.07, and a silver chloride content of 99.5 mol%.

The above silver halide emulsion EMP-1 was added at 6 O'C with the following compounds. Appropriate chemical reaction was performed. Similarly, after optimally chemically sensitizing the silver halide emulsion EMP-1B, the silver halide emulsion EMP-1 and the silver halide emulsion EMP-1B were mixed in a silver content ratio of 1: 1. : 1 to obtain a red-sensitive silver halide emulsion (101 R).

Chio sulfate isocyanatomethyl Riumu 1 X 1 0- ⁴ mol / mol A g X chloroauric acid 2 X 1 0- ⁴ mol / mol A g X Stabilizer: STAB- 1 3 X 1 C ⁴ mol / mol A g X stabilizer : STAB- 2 3 X 1 0- ⁴ mol / mol A g X stabilizer: STAB- 3 3 X 1 0- ⁴ mol / mol A g X sensitizing dyes: RS- 1 1 X 1 0- ⁴ mol / mol A g X sensitizing dyes: RS - 2 1 X 1 0- 4 mol / mol A g X

S T A B- 1-(3 _acetoamidophenyl) 1-5-mercaptotetrazole

S TA B—2: 1—Phenyl-5-Mercaptotetrazole

S TAB— 3: 1— (4-ethoxyphenyl) -1-5-mercaptotetrazo

To the red-sensitive emulsion, SS-1 was added in an amount of 2.0 × 10 ³ per mole of silver halide.

(Preparation of green photosensitive silver halide emulsion)

In the preparation of the above silver halide emulsion EMP-1, the average particle size was 0 in the same manner except that the addition time of (Solution A) and (Solution B) and the addition time of (Solution C) and (Solution D) were changed. A silver halide emulsion EMP-2 was obtained as a monodisperse cubic emulsion having a length of 40 m, a coefficient of variation of 0.08 and a silver chloride content of 99.5%. Then, the silver halide milk In the preparation of EMP-1, the average particle size was 0.50 / m2 except that the addition time of (Solution A) and (Solution B) and the addition time of (Solution C) and (Solution D) were changed. A silver halide emulsion EMP-2B was obtained as a monodisperse cubic emulsion having a coefficient of variation of 0.08 and a silver chloride content of 99.5%.

The silver halide emulsion EMP-2 prepared above was optimally chemically sensitized at 55 ° C using the following compounds. Similarly, after optimally chemical sensitizing the silver halide emulsion EMP-2B, the sensitized silver halide emulsion EMP-2 and the silver halide emulsion EMP-2B were added to the silver content. The mixture was mixed at a ratio of 1: 1 to obtain a green-sensitive silver halide emulsion (101 G).

Sodium sodium thiosulfate 1 X 10 ^_4 mol mol Ag X Chloroauric acid 1.2 X 1 O ⁴ mol mol Ag X Stabilizer: STAB—12.5 X 10_ ⁴ mol / mol Ag X stabilizer : S tAB- 2 3. 1 X 10- 4 Morunomoru A g X stabilizer: S tAB- 3 3. 1 X 10- 4 mole mol A g X sensitizing dyes: GS- 1 ⁴ X 10- 4 mol / mol A g X

(Preparation of blue-sensitive silver halide silver halide emulsion)

In the preparation of the silver halide emulsion EMP-1, the average particle diameter was 0 in the same manner except that the addition time of (Solution A) and (Solution B) and the addition time of (Solution C) and (Solution D) were changed. A silver halide emulsion EMP-3 was obtained as a monodisperse cubic emulsion having a particle size of 7.1 m, a coefficient of variation of 0.08, and a silver chloride content of 99.5%. In addition, in the preparation of the silver halide emulsion EMP-1 described above, except that the addition time of (Solution A) and (Solution B) and the addition time of (Solution C) and (Solution D) were changed, Silver halide, a monodisperse cubic emulsion with an average grain size of 0.64 ^ m, a coefficient of variation of 0.08, and a silver chloride content of 99.5% Emulsion EMP-3B was obtained.

The above silver halide emulsion EMP-3 was optimally chemically sensitized at 60 ° C using the following compounds. Similarly, after optimally chemically sensitizing silver halide emulsion EMP-3B, silver halide emulsion EMP-3 and silver halide emulsion EMP-3B were combined with silver halide emulsion EMP-3B. The mixture was mixed at a ratio of 1: 1 in a quantitative ratio to obtain a blue-sensitive silver halide emulsion (101B).

Chio sodium sulfate 1 X 10- ⁴ mol / mol A g X chloroauric acid 1. 2 X 10- ⁴ mol / mol A g X Stabilizer: STAB- 1 2 X 1 CI- ⁴ mol / mol A g X stabilizer : STAB- 2 2. 4 X 1 Ο- 4 mol Z moles A g X stabilizer: STAB - 3 2. 1 X 10- 4 mol / mol A g X sensitizing dyes: BS- 1 X 10- ⁴ mole / mol A g X sensitizing dye: BS- 2 1 X 10- ⁴ mol / mol A g X

(C ₂ H ₅ ) 3 GS-1

[Preparation of Sample 101]

A reflective support in which high-density polyethylene was laminated on both sides of a paper pulp having a basis weight of 180 g Zm ² was produced. However, on the side to which the photosensitive layer was applied, a molten voltylene containing a surface-treated anatase type titanium oxide dispersed at a content of 15% by mass was laminated. The mass of the obtained support was 220 g Zm ² . After subjecting this reflective support to corona discharge treatment, a gelatin undercoat layer was provided, and each layer having the following structure was further provided thereon, to prepare Sample 101 as a silver halide color photographic light-sensitive material. The coating solution was prepared as described below.

(Preparation of first layer coating solution)

Yellow coupler (Y-1) 23.4 g, dye image stabilizer (ST-1) 3.34 g, (ST-2) 3.34 g, (ST-5) 3.34 g, stin prevention 0.34 g of agent (HQ-1), 5.0 g of image stabilizer A, 3.33 g of high-boiling organic solvent (DBP) and 1.67 g of high-boiling organic solvent (DNP) and ethyl acetate 60 m 1 And disperse the solution in 220 ml of a 10% aqueous gelatin solution containing 7 ml of 20% surfactant (SU-1) using an ultrasonic homogenizer to prepare a yellow coupler dispersion. did. The yellow coupler dispersion was mixed with the blue-sensitive silver halide emulsion (101B) prepared above to prepare a first layer coating solution.

(Preparation of coating solution for 2nd to 7th layers)

The coating solutions for the second to seventh layers were also prepared using the following additives in the same manner as in the preparation method of the first layer coating solution.

(Each layer configuration)

7th layer: protective layer> gZm ² gelatin 0.70 DI DP 0.005 silicon dioxide 0.003

Gelatin 0.30 UV absorber (UV-1) 0.12 UV absorber (UV-2) 0.04 UV absorber (UV-3) 0.16 Sting inhibitor (HQ-5) 0.04 PVP Mouth lid) 0.03 Anti-irradiation dye (AI-1) 0.01 layer 5th layer: red-sensitive layer>

Gelatin 1.20 Red-sensitive silver halide emulsion (10 1 R) 0.21 Cyan coupler (C-1) 0.25 Cyan coupler (C-2) 0.08 Dye image stabilizer (ST-1) 0.10 Sting inhibitor (HQ-1) 0.004

D B P 0.10 D 0 P 0.20

<4th layer: UV absorbing layer>

Gelatin 0.90 UV absorber (UV-1) 0.28 UV absorber (UV-2) 0.09 UV absorber (UV-3) 0.38 Anti-stinting agent (HQ-3) 0.110 Anti-dye (AI-1) 0.02 Third layer: Green photosensitive layer> Gelatin 20 Green light-sensitive silver halide emulsion (101 G) 0 14 Magenta coupler (M-1) 0 20 Dye image stabilizer (ST-3) 0 20 Dye image stabilizer (ST-4) 0, 17 DIDP 0, 13 DBP 0, 13 Anti-irradiation dye (AI-2) 0.01 <Second layer: intermediate layer>

Gelatin 10 Anti-stinning agent (HQ-2) 03 Anti-stinting agent (HQ-3) 03 Anti-stinning agent (HQ-4) 0 05 Anti-stinting agent (HQ-5) 0, 23 DIDP 0,06 Optical brightener (W-1) 0,10 Anti-irradiation dye (AI-3) 0.0 <First layer: blue-sensitive layer>

Gelatin 10 Blue light-sensitive silver halide emulsion (101 B) 0.26 Yellow coupler (Y-1) 0.7 Dye Image stabilizer (ST- :!) 0.10 Dye Image stabilizer (ST-2) 0.10 Sting inhibitor (HQ-1) 0.01 Dye image stabilizer (ST-5) 0.10 Image stabilizer A 0.15 DNP 0.05 DBP 0.10 Support: Reflective support Polyethylene laminate Toner paper (containing a trace amount of colorant) The amount of each of the silver halide emulsions described above was expressed in terms of silver. Also, (H-1) and (H-2) are added to each of the above coating solutions as a hardening agent, and the following surfactant (SC-1) is added as a coating aid, The tension was adjusted.

S U-1: Tree i-sodium propylnaphthalenesulfonate

S C-1: Sodium decyl sulfonate

DBP: dibutyl phthalate

DN P: dinonyl phthalate

DOP: Dioctylphthalate

D I D P: di-i-decyl phthalate

H—1: Tetrakis (vinylsulfonylmethyl) methane

H—2: 2,4-dichloro-1-6-hydroxys-triazine-sodium

HQ— 1: 2,5—G-t-octyl high droquinone

HQ—2: 2,5—Gee sec—Dodecylhydroquinone

HQ—3: 2,5-di-sec-tetradecylhydroquinone

HQ—4: 2—sec-dodecinole 5—sec-tetradecinoledidroquinone

HQ-5: 2,5-di [(1,1-dimethyl-1-hexyloxycarbonyl) Butyl] hydroquinone

Image stabilizer A: P-t-octylphenol

Y one 1

-1

C-1

C-2

ST— 1

ST—:

ST— 3

o ₂ s OC ₁₃ H ₂₇ (i)

ST— 4

ST— 5

UV-1

UV-2

UV-3

AI-1

AI-2

AI-3

W-1

The total iron content of the binder (gelatin) of sample 1 prepared above was measured by atomic absorption spectrometry and was found to be 45 ppm, and the total calcium content was determined by ICP emission spectrometry to be 21 Omg / It was m ^2. The total amount of gelatin is 6.5 g / m "m.

[Production of Samples 102 to L08]

In the preparation of sample 101, the total content of iron and calcium in the gelatin used in all layers (changed the type of gelatin: lime-treated bone gelatin subjected to ion exchange was used), and the total amount of gelatin (1st The amount of gelatin in the blue-sensitive layer, which is the layer, was adjusted) and the type of surfactant added to all layers (the amount added was the same as that of SC-1 in Sample 101) was changed as shown in the table below. Samples 102 to 108 were prepared in the same manner except for the above. In the table below, S agent: surfactant, Ca: calcium, Gel: gelatin. Sample Iron content C a content SA agent Total G e 1 amount Remarks No.ppmmg X m "g / m

10 1 4 5 2 10 SC—16.5 Comparative Example 102 8 2 1 0 SC—16.5 Inventive 103 4 2 10 SC—16.5 Inventive 104 49 SC—16.5 Inventive 105 4 9 S-365 The present invention 106 4 7 S-36 1 The present invention 107 3 7 S—35 7 The present invention 108 3 7 * S-3 / N-85 7 The present invention S— 3: Isopropyl Naphthalenesulfonic acid

*: Exemplified compound S-3 and Exemplified compound N-8, which is a nonionic surfactant, were used in a mass ratio of. Each of the samples obtained as described above was exposed to white light through an optical wedge with an exposure time of 0.5 seconds through a conventional method, and then subjected to a developing process in the following developing process. Treatment process Treatment temperature Time Replenishment amount

Color development 35.0 ± 0.3 ° C 45 seconds 80ml / m ^:

Bleaching and fixing 35.0 ± 0.5 ° C 45 seconds 2 15 m 1 / m 'Stabilization 30-34 ° C 60 seconds 248m l m

Drying 60-80 ° C 30 seconds

The composition of the developing solution is shown below. [Color developer tank solution and replenisher] Tank solution Replenisher Pure water 800 ml 800 ml l Triethylene diamine 2 g 3 g Diethylene glycol 10 g 10 g Bromium rim 0.01 g

3.5 g of potassium chloride

Sulfuric acid lime 0.25 g 0.5 g

N-Ethyl-1-N- (1-methanesulfonamidoethyl) -1-3-methyl-14-aminoaniline sulfate 6.O g 10.0 g N, N-Jetylhydroxylamine 6.8 g 6.O g Liethanolamine 10. Og 10.0 g Diethylenetriaminepentaacetic acid pentasodium salt 2. Og 2.0 g Optical brightener (4, 4'-diaminostilbene disulfonic acid derivative)

2.0 g 2.5 g Potassium carbonate 30 g 30 g Water was added to bring the total volume to 1 liter.The tank solution was adjusted to pH = 10.0 and the replenisher was adjusted to pH = 10.60. .

(Bleach-fixer tank solution and replenisher)

Ferric ammonium diammonium pentaacetate dihydrate 65 g Dethylene triammonium pentaacetic acid 3 g ammonium thiosulfate (70% aqueous solution) 100 ml 2-amino-1,5-mercapto-1,3,4-thiadiazole 2. 0 g ammonium sulfite (40% aqueous solution) 27.5 m 1 Water was added to bring the total amount to 1 liter, and the pH was adjusted to 5.0 with carbonated lime or glacial acetic acid.

(Stabilizing solution tank solution and replenisher solution)

o _ phenyl phenol 1.0 g

5-Methyl 1-Methyl 4-Isothiazolin-3-one 0.02 g 2-Methyl 4-isothiazolin-3-one 0.02 g Diethylene glycol 1.0 g Optical brightener (Tinopearl SFP) 2. 0 g 1—Hydroxyshethylidene 1,1-diphosphonic acid 1.8 g Bismuth chloride (45% aqueous solution) 0.65 g Magnesium sulfate · 7-hydrate 0.2 g PVP (Polyvinylpiridone) 1. 0 g ammonia water (25% aqueous ammonium hydroxide solution) 2.5 g tri-triacetate / sodium trisodium salt 1.5 g Add water to make 1 liter, pH = 7 with sulfuric acid or aqueous ammonia Adjusted to 5.

At this time, the amount of the overflow solution from the color developing solution was 75 ml for the processing of 1 m ² of the light-sensitive material.

Next, as described in JP-A-7-234487, the replenisher of the color developing solution was regenerated as shown below, and the regenerating replenisher was subjected to a running treatment with a replenishment amount of 40 m 1 / m ^2. I went.

(Method of regenerating color developer)

Stock the overflow solution of the color developer (stock solution) and add 16 L of replenisher. The stock volume at the time of replenishment was 9.8 L. Next, the following chemicals were added to 9.8 L of the stock solution, and water was added to make the solution 16 and reused as a regeneration replenisher.

(Formulation of replenisher)

Stock solution 9.8 L N-Ethyl-N- (| 3-Methanesulfonamidoethyl) 1-3-Methyl-41-aminoadiline sulfate 57 g

N, N-Jetylhydroxylamine 56 g Triethanolamine 93 g Diethylenetriaminepentaacetic acid sodium salt 12 g Fluorescent whitening agent (4,4'-diaminostilbenesulfonic acid derivative) 16 g Carbonate 186 g Water Was added to make the total amount 16 liters, and adjusted to 1 £ = 10.60 at 011.

This regeneration treatment was repeated 20 times for each of the samples 101 to 108. That is, the number of rounds is 40. The recall rate was set at 100%.

《Evaluation》

For the evaluation, after treating each of the above samples with 500 m ² , the blue light reflection density (D min stain) of the white background was measured using an optical densitometer (X-Rite 310 TR). The results obtained are shown in the table below. Sample No.Stin Remarks

D m 1 n

1 0 1 0 1 1 2 Comparative example

1 02 0, 093 The present invention

1 03 0, 0 87 The present invention

1 04 0 084 The present invention

1 05 0, 0 82 The present invention

1 06 0, 0 80 The present invention

1 07 0, 0 79 The present invention

From the above table, it can be seen that the silver halide photographic light-sensitive material in which the total iron content of the binder (gelatin) according to the present invention is in the range of 0.01 to 10 ppm, Even with the use of, the occurrence of stin on a white background was small, and a good image was obtained. This is an unexpected effect of the prior art. Industrial potential

As described above, according to the present invention, it is possible to provide a method for processing a silver halide photographic light-sensitive material in which the occurrence of stin on a white background is reduced even when processing is performed using a regenerating processing solution.

Claims

The scope of the claims

1. A method for processing a silver halide photographic light-sensitive material having a binder on a support, wherein the iron content of the binder is 0.01 to 10 ppm, and the silver halide photographic light-sensitive material is imagewise A reflow of an overflow solution of a color developing solution at the time of continuous processing after exposure to light, and using the regenerated color developing solution for processing of the silver halide photographic light-sensitive material. Processing method of silver photographic photosensitive material.

2. The total calcium content of the silver halide photographic light-sensitive material, according to claim 1, characterized in that 0.5 a 0 1~1 O m gZm ² halogen Kagin'utsushi true photographic material Processing method.

3. The method according to claim 1, wherein the silver halide photographic material contains an anionic surfactant having a benzene ring or a naphthalene ring. Processing method of silver photographic photosensitive material.

4. The method according to claim 1, wherein at least one kind of the binder is gelatin, and a total content of the gelatin is 6.2 g / m ² or less. Or the method for processing a silver halide photographic light-sensitive material according to item 1.

5. The silver halide photographic light-sensitive material according to any one of claims 1 to 4, wherein the silver halide photographic light-sensitive material contains a nonionic surfactant. Processing method.